Printing process for textiles



Patented Nov. 20, 1945 PRINTING PROCESS FOR TEXTILES Q-Alexis Wiazmltinow, Basel, Switzerland, asslgnor to Sandoz A. G., Fribourg, Switzerland No Drawing.- Application October 28, 1941, Serial I No. 416,909. In Switzerland November 20,

8 Claims ,The present invention relates to an improved textile printin process with leuco ester salts. of vat dyestuffs. .i j

It isknownthat semantic-5 ester salts o1 vat dyestuffs such as Indigos'ol Green 13 (see Schultz,-

Farbsto'fitabellen, 2d v0l'.,"page{,133), Indigosol- .gr raeand Oliv'G'reen 'IB (see Schultz,

Farbstofftabellen;complemental vol. II, page 209), Indigosol Red IFBB (see Schultz, Farbstofftabellen, complemental volfII, page 209), Indigosol Brilliant Violet 14R give unsatisfactory results in printing; whendeveloped by' one of theknown steaming developing processes, especially on regeiie'ratd cllul6' 'sucli as rayon crepe, ,vistra mous'seli'nd'Be'mberg silk and the like. Especially printirfg's obtained with'f Indigosol Green IB,-In-

digosol Green; IGG andJIndig'osol Olive Green 13 are verypoor. It" is believed thatthis behaviour gf thes'e dy'estufis'is due to their ready cleavage andeto the size of the particles. The practical tests in the textile printing industry have shown that. the above named Indigosol dyestuffs can satisfactorily be fixed on fibres Ofregenerated cellulose, when theylare first subjected to a pre yious steaming and afterwards developed by the so calledwet developing processes, like thenitrite process. 'lh 'previous steaming makes it pos sible for these dyestuffs topenetrate into the fibre before they heeon'ie split andfor the fixation or the lndigosolstotake place inthe inner parts pithe fibre when they become developed.

;;Inorder to obviate the taking place of an undue rapid splitting of the Indigosols during the steaming process; it is necessary to reduce in the printed pastes the qriantity'bf the'acid splitting agents, suchas animonium= thiocyanate, diethyltartrate, et f oxidising agents such as sodium chlorate, amnidn urnjchlorate and of catalysts such as ammoni'ui'n vanadate'. These changes of the printing recipe require an increase of the duration of fore, their bad fixation in printing on fibres from natural and regenerated cellulose can be avoided by adding to the printing pastes containing besides the leuco ester salts, a certain amount of oxidising agents, of acid splitting agents, of cata- V lysts and of other usual additions, such organic bases that are stable towards the oxidising agents in absence of inorganic acids and by printing this paste on the fabrics and developing the dyestuffs by a short steaming. "By' the addition of the above cited bases a rapid-and satisfactory fixation of thedyestuifs generated from the leuco esters is obtained; without any previous splitting taking place. The printings obtained in this way are much deeper thanthose obtainedby any of the known steam-developing processes. The printing pastes containing the above said bases are further more stable than the usual printing pastes, which is naturally of great importance where easily cleavable Indigosols are used.

--As organic bases that are especially suitable for-carrying out the present process can be cited the aliphatic bases like mono-, diand triethanolamine, diethylmonoethanol amine, monoethanolethylenediamine, diethylenetriamine, .triethylene tetramine, as cycloaliphatic bases, -for example hexahydroaniline, as aromatic bases aniline, N- ethylglycerylaniline and N-diglycerylaniline, and as heterocyclic bases pyridine, piperazine and the like. If the base employed is easily soluble in water, it can be directly added to the already the steaming operation from 15 minutes to about 45. t 60Ylninutes,-' otherwise the Indigosols would not be split at all. Such 'along steaming process is-generally not desired and especially in such cases where the fabricshave been printed notonly withfiIndigosols, but with other dyestuffs, such as Rapidogenor Rapidecht'dyestuffs, which become more or less destroyed by a long steamingoperation and do notgive brilliant prints. Although the steaming operation is extended, the prints 0b-' tained. with the-[Indigosols by this method are fofsthe leuco ester salts of vat dyestuffs and, there- 1 prepared printing paste. In cases where the base is not easily soluble, it is preferable to dissolve it in a solvent such as ethanol, thiodiglycol and the like and to add its solution to the printing paste.

a The fabrics from cellulose or regenerated cellulose printed with the printing pastes prepared as above described are after printing dried in the usual manner and steamed for 10-30 minutes, whereby a good penetration and development of the leuco esters will be obtained. The printings thus obtained do not bleed during soaping operation and give full brilliant patterns. It is obvious that the quantity-of. the acid. splitting agent, of the oxidizing agent and of the catalysts must be adopted to the steaming equipment and steaming method used in the respective printing house. Generally it can be said, that an increase of the quantity of the acid splitting agents will reduce the time of steaming whichhas been increased by the addition of the base,

The prints obtained according to the presen process are superior in respect of the yield. of the. dyestufi's to the generally known developing processes such as the sol-developing process. the

chlorate developing process, the ammonium thiocyanate-chlorateand ammoniumchlorate steam processes and sometimes also the so-called nitrite process.

The present process further presents the great advantage of being able to be combined: with the use of other dyestufis, because the steaming operation is very short and without influence on other dyestuffs like the Rapidogen and Rapidecht dyestuffs.

The following examples, without'being limitative, illustrate the present prooesstl'le by weight:

Example 1 digosol Green IB (Schultz, Farbstofitabellen, 2nd

vol., page 133) with a printing'paste of the fol-r.

lowing oomposition:

The following table showsa series of organic 5 bases that can be used and how long the printing fabric must be steamed in each case: I

. Organic base i Y period Minute:

ZOpm-ts ol-triethanolsmine i parts of diethylmonoethanolamine.- 20 parts of tetmethanolammonium-hyd lO parts of pyridine. r 20 parts of N-ethylglycerylan ne dissolved n 20 parts of alcohol 20 patrts oi N-diglyoerylaniline dissolved in 20 parts of 20 parts of hexahydroaniline c 20 parts 01 piperazine 20 parts of monoethanolethylonedmmino. 20 parts of diethanolamine. 20 parts of monoethimolamin 20 parts of anilineg;

assesses;- s 5852 The prints obtained with the 'aboveoited printing pastes are after drying steamed for 10-30 minutes, rinsed, soaped at boiling temperature; rinsed again and dried. The prints obtained in this manner are much deeper thanthose which are obtained by the so-oalled ammonium. thiocyanate steaming process.

Example 2 Vistra mousselineis printed with a printing paste of the following composition:

A piece of vistra mousseline is printed witli'In-Q}- I Steaming Example 3 (A piece of vistra fabric is printed with Indigosol .Green-IGG, iIndigosol Olive Green IB (Schultz,

Earbstoiftabellen,,complemental vol. II, page 209) J and Indigosollted IFBB (Schultz, Farbstofitabellen, complemental vol II, page 209) in printing pastes of thefollowing compositions:

Parts Indigosol Green IGG a0 DehagenO (see Example 1)----" 100 Hotwater; o -.210 Neutral starch tragacanth thickening..' 500. Sodium chlorate solution of 25% 50 Ammoniumvainadatesolution of 1 l Diethyl tartrate .40 Diethylenetriamine V 10 IndigosolBed 'IF'BB 70 Thiodiglycol 50 Hot .water. rl 250 Starch tragacanth thickening 495 Diethyltartrate 50 Sodium chlorate solution 25'% Ammonium vanadate solution 1% 20 Diethylenetriamine l0 1 V p r V Parts Indigosol OiiveGreen IB .50 Dehagen 0 (see. Example 1) 100 Diethyltartrate '.-Tf """I" '-1"T? --Z""'--""' Neutral starch tragacanth thiekening. $70 Sodium chlorate solution 0i! 25% 80 Ammonium vanadate solution o f\ 1% 20 Diethylenetriamine 10 The prints obtained with the above cited pastes are after drying steamed during 15-20 minutes, rinsed, soaped at boiling temperature, rinsed again "and dried. The prints obtained with these pastes are much deeper than those which can be obtained by the known steam developing process.

Example 4 A piece of Vistra-mousseline is printed with Indigos'ol Brilliant Violet'l lR. in a printing paste of the following composition:

f Part5 Indigosol Brilliant Violet 14R 50 Thiodiglycol 50 Dehagen 0' (see Ebzample'l) 100 Diethyltartrate so Hot water 200 Neutral starch tragaoanththickening 440 Sodium chlorate solution'of 25% 60 Ammonium vanadate solution of 1% 20 Triethanola'mine' 20 Sodium sulphoxylate-iorgnaldehyde 10 The prints are steamed for 10 to 15 minutes, rinsed, soaped at boiling temperature, rinsed again and dried, The print obtained according to this composition is much deeper than those which can be obtained by the well-known steam developing processes.

What I claim is:

1. A printing paste for textile of cellulosic nature, comprising an alkali metal salt of a sulfuric acid ester of a leuco-vat-dyestufi, an oxidising agent, an agent capable of splitting ofi acid and a catalyst and containing at least one volatile organic base which is stable towards the oxidising agent in absence of an inorganic acid, said printing paste allowing the production of deeper and fuller shades on the said textiles by a short steaming process as compared to the shades obtained by the known developing processes.

2. A printing paste for textiles of cellulosic nature, comprising an alkali metal salt of a sulfuric acid ester of a leucovatdyestufi, an oxidising agent, an agent capable of splitting ofi acid, a catalyst and triethanolamine, said printing paste allowing the production of deeper and fuller shades on the said textiles by a short steaming process as compared to the shades obtained by the known developing processes.

3. A printing paste for textiles of cellulosic nature, comprising an alkali metal salt of a sulfuric acid ester of a leuco-vat-dyestuft, an oxidising agent, an agent capable of splitting oflf acid, a catalyst and diethylenetriamine, said printing paste allowing the production of deeper and fuller shades on the said textiles by a short steaming process as compared to the shades obtained by the known developing processes.

4. A printing paste for textiles of cellulosic nature, comprising an alkali metal salt of a sulfuric acid ester of a leuco-vat-dyestuff, an oxidising agent, an agent capable of splitting off acid, a catalyst and monoethanolethylenediamine, said printing paste allowing the production of deeper and fuller shades on the said textiles by a short steaming process as compared to the shades obtained by the known developing processes.

5. A process for producing deep and full shades by printing leuco ester salts of vat dyestuffs on cellulosic fabrics, comprising the step of subjecting to a short steaming cellulosic fabrics printed with a printing paste comprising an alkali metal salt of a sulfuric acid ester of a leuco-vat-dyestuff, an oxidising agent, an agent capable of splitting off acid, a cataylst and a volatile organic base which is stable to the oxidising agent in presence of an inorganic acid.

6. A process for producing deep and full shades by printing leuco ester salts of vat dyestuffs on cellulosic fabrics, comprising the step of subjecting to a short steaming cellulosic fabrics printed with a printing paste comprising an alkali metal salt of a sulfuric acid ester of a leuco-vat-dyestufi, an oxidising agent, an agent capable of splitting ofi acid, a catalyst and triethanolamine.

7. A process for producing deep and full shades by printing leuco ester salts of vat dyestufis on cellulosic fabrics, comprising the step of subjecting to a short steaming cellulosic fabrics printed with a printing paste comprising an alkali metal salt of a sulfuric acid ester of a leucovat-dyestufi, an oxidising agent, an agent capable of splitting off acid, a catalyst and diethylenetriamine.

8. A process for producing deep and full shades by printing leuco ester salts of vat dyestuffs on cellulosic fabrics, comprising the step of subjecting to a short steaming cellulosic fabrics printed with a printing paste comprising an alkali metal salt of a sulfuric acid ester of a leuco-vat-dyestuif, an oxidising agent, an agent capable of splitting ofi acid, a catalyst and monoethanolethylenediamine.

ALEXIS W'IAZMITINOW. 

